Catalytic Distillation Technologies

Mario J Maraschino

Willibrord A Groten

Gary G Podrebarac

Montri Vichailak

Bertrand R Klussman

Mitchell E Loescher

Christopher C Boyer

Kerry L Rock

A process for the production of tertiary ethers, including: feeding a hydrocarbon stream comprising isoolefins and propionitrile to a distillation column reactor system containing at least one etherification reaction zone; feeding a Cto Cmonoalcohol or mixture thereof to the distillation column reactor; concurrently in the distillation column reactor system: reacting a portion of the isoolefins with a portion of the alcohols to form a tertiary ether; and separating the tertiary ether from unreacted isoolefins; withdrawing the tertiary ether and propionitrile from the distillation column reactor system as a bottoms; withdrawing the unreacted isoolefins from the distillation column reactor system as an overheads; and operating the distillation column reactor system such that the etherification reaction zone is substantially free of propionitrile.

Method of producing tertiary amyl ethyl ether

A process for reacting a first component with itself or a second component to produce a third component in which a first material comprising a first component or said first component and a second component is fed to divided wall column having a catalytic distillation structure in at least one of the separate vertical sections of the divided wall column where concurrently: (1) a first component alone or with a second component is contacted with a catalytic distillation structure in a distillation reaction zone thereby catalytically reacting at least a portion of the first component with itself or with the second component to form a product and (2) a first mixture comprising the first component and the product or the first component, the second component and the product; and withdrawing the product from the distillation column reactor; while within the column concurrently with the catalytic reaction and fractionation a second mixture is fractionated, which contains the first component and the product or first and second components (if a second component is present) and the product in a parallel and separate distillation non reaction zone to fractionate the product and withdrawing the product from said distillation non reaction zone. For example, tertiary amyl methyl ether may be prepared by reacting methanol with isoamylene in a Cstream utilizing a distillation column reactor wherein the distillation column reactor comprises one side of a divided wall column. On one side the product, tertiary amyl methyl ether, is separated from the unreacted methanol and C's and on the other side the remaining isoamylenes are reacted with methanol and a separation of the tertiary amyl methyl ether and C's from the methanol/Cazeotrope is effected.

Process and apparatus for catalytic distillations

A process for concurrently fractionating and hydrotreating a full range naphtha stream. The full boiling range naphtha stream is subjected to simultaneous hydrodesulfurization and splitting into a light boiling range naphtha and a heavy boiling range naphtha, which have been treated to convert mercaptans in the fractions to HS, which is separated with and separated from the light naphtha which is further hydrodesulfurized by contacting the light boiling range naphtha with hydrogen in countercurrent flow in a fixed bed of hydrodesulfurization catalyst to remove recombinant mercaptans which are formed by the reverse reaction of HS with olefins in the naphtha during the initial hydrodesulfurization wherein the improvement comprises fractionating said portion of light boiling range naphtha to remove a lighter fraction thereof from said countercurrent flow reactor before contact of said lighter fraction with said fixed bed catalyst, because the lighter fraction is substantially free of mercaptans and is not benefitted by further treatment.

HDS process using selected naphtha streams

A process is disclosed for preparing a Cstream for feeding to an alkylation process which reacts isobutane with butene to produce isooctane. The Cstream is treated in a first distillation column reactor to remove dienes and mercaptans and separate out any C's which might be present. The treated C's are then fed to a second distillation column reactor that concurrently isomerizes 1-butene to 2-butene and splits the normal C's from the iso C's. The iso C's are then fed to a third distillation column reactor where a portion of the isobutene is saturated to isobutane. The C's from the isomerization/splitter are combined with the C's from the hydrogenation unit and fed to a cold acid alkylation unit. The third distillation column may also oligomerize a portion of the isobutene to diisobutene in the upper end which is saturated in the bottom of the column to isooctane.

Process for the utilization of refinery C4 streams

A process is disclosed for preparing a Cstream for feeding to an alkylation process which reacts isobutane with butene to produce isooctane. The Cstream is treated in a first distillation column reactor to remove dienes and mercaptans and separate out any C's which might be present. The treated C's are then fed to a second distillation column reactor that concurrently isomerizes 1-butene to 2-butene and splits the normal C's from the iso C'S. The iso C's are then fed to a third distillation column reactor where a portion of the isobutene is saturated to isobutane. The C's from the isomerization/splitter are combined with the C's from the hydrogenation unit and fed to a cold acid alkylation unit. The third distillation column may also oligomerize a portion of the isobutene to diisobutene in the upper end which is saturated in the bottom of the column to isooctane.

A process for the desulfurization of a light boiling range (C -350&deg; F.) fluid catalytically cracked naphtha, which may be first subjected to a thioetherification to react the diolefins with mercaptans contained in it to form sulfides, is fed to a high pressure (>250 psig) catalytic distillation hydrodesulfurization step along with hydrogen under conditions to react most of the organic sulfur compounds, including sulfides from the thioetherification to form H S. The H S and a light product stream (C 's and C 's) are removed as overheads. The bottoms from the catalytic distillation hydrodesulfurization step is fractionated and the bottoms from the fractionation contacted with hydrogen in a straight pass hydrogenation step in the presence of a hydrodesulfurization catalyst at pressure of >250 and temperature >400&deg; F. to further reduce the sulfur content.

Process for the desulfurization of a light FCC naphtha

A process for concurrently fractionating and hydrotreating of a full range naphtha stream. The full boiling range naphtha stream is subjected to simultaneous hydrodesulfurization and splitting into a light boiling range naphtha and a heavy boiling range naphtha, which have been treated to covert mercaptans in the fractions to H S, which is separated with and separated from the light naphtha wherein the improvement is a further hydrodesulfurization by contacting the light boiling range naphtha with hydrogen in countercurrent flow in a fixed bed of hydrodesulfurization catalyst to remove recombinant mercaptans which are formed by the reverse reaction of H S with olefins in the naphtha during the initial hydrodesulfurization.

Process for simultaneous hydrotreating and splitting of naphtha streams

An apparatus and process for treating a complex mixture of hydrocarbons containing undesirable olefinic compounds to remove the mono olefins and diolefins in two stages and separate a desirable key component from the mixture, by first treating the key component in a reactive distillation column under mild conditions to hydrogenate diolefins then separating the diolefin-depleted key component and any lighter materials from the heavier components and sending the diolefin-depleted key component and lighter materials to a second reactive distillation column where the lights are removed overhead and the diolefin-depleted key component is hydrogenated under more severe conditions to remove the mono olefins.

Apparatus and process for hydrogenations

An apparatus for conducting reactive distillations comprising a first distillation column, a first primary catalyst bed for carrying out a hydrogenation of unsaturated compounds comprising diolefins. The first primary catalyst bed is positioned in the distillation column to provide a first reaction zone for diolefins, and optionally, a first secondary catalyst bed above the first primary catalyst bed is provided as a second reaction zone for diolefins remaining in the first distillation column after the first reaction zone. A mixed saturated/unsaturated compound feed entry is provided below the first primary bed with a hydrogen feed below the primary bed. An overhead line connects to a second distillation column comprising a second primary catalyst bed for carrying out hydrogenation of unsaturated compounds comprising mono olefins from said first distillation column. The second primary catalyst bed is positioned in the second distillation column to provide a first reaction zone for unsaturated compounds, and optionally, a second secondary catalyst bed below the second primary bed provides a second reaction zone for mono olefins remaining in the second distillation column after the first reaction zone. The overhead line from the first distillation column connects to the second distillation column above the second primary catalyst bed and a hydrogen feed enters below the second primary bed.

A process for selectively treating the components in a multi-component stream in a distillation column reactor. Additional catalytic distillation structures are placed as a secondary bed in the distillation column, either above or below the primary bed, and the selected component withdrawn after reaction in the primary bed to prevent its entry into the secondary bed.

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Houston, TX, United States of America

Mario J Maraschino